Percursors to fluoroalkanol-containing olefin monomers, and associated methods of synthesis and use

ABSTRACT

The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted α,β-unsaturated esters. The fluoroalkanol-substituted α,β-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.

RELATED APPLICATIONS

This application claims priority to U.S. patent application Ser. No.10/729,453, filed Dec. 4, 2003, the disclosure of which is incorporatedherein by reference.

TECHNICAL FIELD

This invention relates generally to the fields of polymer chemistry,lithography, and semiconductor fabrication. More specifically, theinvention relates to novel compounds useful as precursors tofluoroalkanol-containing olefin monomers that are capable of undergoingpolymerization to form a polymer suitable for use in a lithographicphotoresist composition, particularly in a chemical amplificationphotoresist composition. The invention also relates to a method forsynthesizing the novel precursors from a substituted olefinic reactantand a fluorinated carbonyl compound, to a method for using theprecursors in the synthesis of fluoroalkanol-containing olefin monomers,and to related methods and compositions.

BACKGROUND OF THE INVENTION

The patterning of radiation-sensitive polymeric films with high energyradiation such as photons, electrons or ion beams is the principal meansof defining high resolution circuitry found in semiconductor devices.The radiation-sensitive films, often referred to as “photoresists”regardless of the radiation source, generally consist of multicomponentformulations that are usually spin-cast onto a desired substrate such asa silicon wafer. The radiation is most commonly ultraviolet light of thewavelengths of 436, 365, 257, 248, 193 or 157 nanometers (nm), or a beamof electrons or ions, or “soft” x-ray radiation, also referred to as“extreme ultraviolet” (EUV) or x-rays. The radiation is exposedpatternwise and induces a chemical transformation to occur that rendersthe solubility of the exposed regions of the films different from thatof the unexposed areas when the films are treated with an appropriatedeveloper, usually a dilute, basic aqueous solution, such as aqueoustetramethylammonium hydroxide (TMAH).

Photoresists are generally comprised of a polymeric matrix, aradiation-sensitive component, a casting solvent, and other performanceenhancing additives. The highest performing photoresists in terms ofsensitivity to radiation and resolution capability are the group ofphotoresists termed “chemically amplified.” Chemically amplifiedphotoresists allow for high resolution, high contrast, and highsensitivity that are not afforded in other photoresists. Thesephotoresists are based on a catalytic mechanism that allows a relativelylarge number of chemical events such as, for example, deprotectionreactions in the case of positive photoresists or crosslinking reactionsin the case of negative tone photoresists, to be brought about by theapplication of a relatively low dose of radiation that induces formationof the catalyst, often a strong acid. The nature of the functionalgroups that comprise the polymeric matrix of these photoresists dictatesthe tone of the photoresist (positive or negative) as well as theultimate performance attributes.

The nature of the polymeric matrix also dictates the suitability of agiven photoresist for exposure with particular radiation sources. Thatis, the absorbance characteristics of a polymer must be carefullyconsidered when designing a material for lithographic applications. Thisis important with optical lithography where polymers are chosen toprovide a relatively transparent matrix for radiation-sensitivecompounds such as photoacid generators (PAGs). Absorbancecharacteristics are also important because the wavelength of radiationused in optical lithography is directly proportional to the ultimateresolution attainable with a photoresist. The desire for higherresolution causes a continuing drive to shorter and shorter radiationwavelengths. For example, the phenolic polymers used for 248 nm imaging,namely derivatives of poly(4-hydroxystyrene) (PHS), are unsuitable foruse with 193 nm radiation as the opacity of these PHS materials at 193nm does not allow for sufficient radiation to create an appropriateimage profile throughout the photoresist film thickness. That is, inorder for photoresists to function properly, their films must betransparent enough at the exposing wavelength to enable sufficient lightto penetrate to the bottom of the film to create usable developed reliefimages.

In addition to exhibiting the requisite transparency at a particularwavelength, it is important that a photoresist polymer be sufficientlypolar so as to ensure solubility in industry standard developers.Polymers having lower solubility in these developers reduce theefficiency of resist development, a significant drawback in themanufacturing process.

There is, accordingly, a need in the art for a cost-effective andcontrollable method for incorporating functionality into polymers toimpart desirable properties, including both polarity (and thussolubility in aqueous acid or base) and transparency at a particularwavelength. U.S. Pat. No. 3,444,148 to Adelman describes polymersprepared by direct polymerization of an alkene hexafluoroalcohol (i.e.,an alkene containing a —C(CF₃)₂—OH group) with a variety of comonomers.The resulting copolymer compositions were found to have desirablecharacteristics relative to homopolymers that did not have anincorporated hexafluoroalcohol (HFA) group. This approach suffers fromlow incorporation of the desired HFA functionality (less than 2 molepercent) and is wasteful of valuable fluorinated monomer.

Incorporation of fluorinated alcohols into polymers for use inphotoresist compositions has recently been described, but theavailability of the requisite materials is limited. An attempt toincorporate an HFA moiety into polymerizable ethylene-containingmonomers (vinyl ethers and some olefins) has been described inInternational Patent Publication Nos. WO 02/079287 A1, WO 01/86352 A2and WO 03/040827 (DuPont). The methodology described in theaforementioned references involves the reaction of a heteroatomnucleophile with hexafluoroisobutene oxide. This restrictive chemistrylimits the structural diversity of target molecules and is not suitablefor the preparation of acrylate or methacrylate monomers.

Accordingly, there is an ongoing need for new compounds and methods thatcan be used to “tailor” the properties of a photoresist composition.Optimally, such compounds and methods would enable preparation of abroad range of polymer structures having desirable properties withoutneed for costly starting materials or complex syntheses. The presentinvention is directed to the aforementioned need in the art, and, inpart, provides compounds and methods that allow for the incorporation offluoroalkylalcohol (i.e., fluorinated hydroxyalkyl or “fluoroalkanol”)groups in a cost-effective, controlled, reproducible manner.

SUMMARY OF THE INVENTION

In a first embodiment, a method is provided for synthesizing an alkenefluoroalkanol, i.e., an alkene containing a semi-fluorinated orperfluorinated hydroxyalkyl group. These alkene fluoroalkanols, whichare new compositions of matter, are particularly useful as startingmaterials in the preparation of polymerizable olefin monomers viasaturated fluorinated polyol intermediates. The alkene fluoroalkanolshave the structure of formula (III)

wherein:

R¹ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl,C₁-C₂₄ alkoxy, and substituted C₁-C₂₄ alkoxy;

R² is selected from hydrogen, C₁-C₂₄ alkyl and substituted C₁-C₂₄ alkyl;

R³, R⁴, and R⁵ are independently selected from hydrogen, C₁-C₂₄ alkyl,and substituted C₁-C₂₄ alkyl, and further wherein any two of R¹, R², R³,R⁴, and R⁵ may be taken together to form a ring;

R^(6A) is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C₁-C₂₄ alkyl,substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino; and

R^(7A) is C₁-C₂₄ alkyl or substituted C₁-C₂₄ alkyl, and further whereinR^(6A) and R^(7A) may be taken together to form a ring, with the provisothat at least one of R^(6A) and R^(7A) is fluorinated. As indicated, R¹and R² can be in either the (E) or (Z) configuration.

The method for synthesizing the alkene fluoroalkanols of the inventioninvolves contacting (a) an olefinic reactant directly substituted on anolefinic carbon atom with a substituted or unsubstituted methyl groupwith (b) a fluorinated carbonyl-containing compound, e.g., a fluorinatedketone, under conditions and for a time period effective to allowaddition of the olefinic reactant to the carbonyl carbon of thefluorinated ketone.

In another embodiment, the invention pertains to fluorinated polyolsthat may be synthesized in a straightforward, one-step hydroborationreaction from the aforementioned alkene fluoroalkanols. The reactioninvolves hydroxylating the alkene functionality in the alkenefluoroalkanol, giving rise to a fluorinated polyol in the form of asaturated fluoroalkanol containing at least one additional hydroxylgroup relative to the alkene fluoroalkanol precursor. Representativefluorinated polyols of the invention have the structure of formula (IV)

wherein:

R¹ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl,C₁-C₂₄ alkoxy, and substituted C₁-C₂₄ alkoxy;

R², R³, R⁴, and R⁵ are independently selected from hydrogen, C₁-C₂₄alkyl, and substituted C₁-C₂₄ alkyl, and further wherein any two of R¹,R², R³, R⁴, and R⁵ may be taken together to form a ring;

R^(6A) is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C₁-C₂₄ alkyl,substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino;

R^(7A) is C₁-C₂₄ alkyl or substituted C₁-C₂₄ alkyl, and further whereinR^(6A) and R^(7A) may be taken together to form a ring, with the provisothat at least one of R^(6A) and R^(7A) is fluorinated; and

one of R¹³ and R¹⁴ is hydroxyl and the other is selected from hydrogenand hydroxyl.

In a further embodiment of the invention, a fluorinated polyol as justdescribed is esterified with an acylation reagent such as an acylchloride, an anhydride, or a carboxylic acid to provide afluoroalkanol-substituted α,β-unsaturated ester such as that having thestructure of formula (V)

wherein:

R¹ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl,C₁-C₂₄ alkoxy, and substituted C₁-C₂₄ alkoxy;

R², R³, R⁴, and R⁵ are independently selected from hydrogen, C₁-C₂₄alkyl, and substituted C₁-C₂₄ alkyl, and further wherein any two of R¹,R², R³, R⁴, and R⁵ may be taken together to form a ring;

R^(6A) is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C₁-C₂₄ alkyl,substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino;

R^(7A) is C₁-C₂₄ alkyl or substituted C₁-C₂₄ alkyl, and further whereinR^(6A) and R^(7A) may be taken together to form a ring, with the provisothat at least one of R^(6A) and R^(7A) is fluorinated; and

one of R¹⁵ and R¹⁶ is hydrogen, and the other has the structure offormula (VI)

in which R¹⁷ is selected from hydrogen, fluoro, C₁-C₄ alkyl, fluorinatedC₁-C₄ alkyl, —CH₂—COOH, —CF₂—COOH, —CH₂—COOR²⁰, and —CF₂—COOR²⁰, R¹⁸ ishydrogen or fluoro, R¹⁹ is hydrogen, fluoro, or —COOH, and R²⁰ is anonhydrogen substituent.

The invention also provides a general method for synthesizing afluoroalkanol-substituted α,β-unsaturated ester which accommodates avariety of reactants and substitutions, the method comprising:

(a) contacting (i) an olefinic reactant directly substituted on anolefinic carbon atom with a substituted or unsubstituted methyl groupwith (ii) a fluorinated carbonyl compound under reaction conditions andfor a time period effective to allow addition of the olefinic reactantto the carbonyl carbon of the fluorinated carbonyl compound, therebyproviding an alkene fluoroalkanol;

(b) hydroxylating the alkene functionality in the alkene fluoroalkanolby subjecting the alkene fluoroalkanol to a hydroboration reaction,thereby providing a saturated fluoroalkanol containing at least oneadditional hydroxyl group;

(c) acylating the additional hydroxyl group by contacting the saturatedfluoroalkanol with an acylation reagent selected from acyl chlorides andanhydrides under esterification conditions.

The fluoroalkanol-substituted esters so provided are polymerizableolefins that can be used to prepare polymers and copolymers havingtransparency at a desired wavelength, e.g., 248 nm, 193 nm, 157 nm, or13.4 nm, such that the polymers and copolymers can be advantageouslyemployed in a lithographic photoresist composition.

DETAILED DESCRIPTION OF THE INVENTION

I. Definitions and Nomenclature

Unless otherwise indicated, this invention is not limited to specificcompositions, components, or process steps. It should also be noted thatthe singular forms “a” and “the” are intended to encompass pluralreferents, unless the context clearly dictates otherwise. Theterminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting.

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

As used herein, the phrase “having the formula” or “having thestructure” is not intended to be limiting and is used in the same waythat the term “comprising” is commonly used.

The term “alkyl” as used herein refers to a linear or branched,saturated hydrocarbon substituent that generally, although notnecessarily, contains 1 to about 24 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl,tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Generally,although again not necessarily, alkyl groups herein contain 1 to about12 carbon atoms, more typically 1 to about 8 carbon atoms. The term“lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and theterm “cycloalkyl” intends a cyclic alkyl group, typically having 3 to 8,preferably 3 to 7, carbon atoms. The term “substituted alkyl” refers toalkyl substituted with one or more substituent groups, i.e., wherein ahydrogen atom is replaced with a non-hydrogen substituent group, and theterms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkylsubstituents in which at least one carbon atom is replaced with aheteroatom such as O, N, or S. If not otherwise indicated, the terms“alkyl” and “lower alkyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing alkyl and loweralkyl, respectively.

The term “alkylene” as used herein refers to a difunctional linear orbranched saturated hydrocarbon linkage, typically although notnecessarily containing 1 to about 24 carbon atoms, such as methylene,ethylene, n-propylene, n-butylene, n-hexylene, decylene, tetradecylene,hexadecylene, and the like. Preferred alkylene linkages contain 1 toabout 12 carbon atoms, more preferred alkylene linkages contain 1 toabout 8 carbon atoms, and the term “lower alkylene” refers to analkylene linkage of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.The term “substituted alkylene” refers to an alkylene linkagesubstituted with one or more substituent groups, i.e., wherein ahydrogen atom is replaced with a non-hydrogen substituent group, and theterms “heteroatom-containing alkylene” and “heteroalkylene” refer toalkylene linkages in which at least one carbon atom is replaced with aheteroatom. If not otherwise indicated, the terms “alkylene” and “loweralkylene” include linear, branched, cyclic, unsubstituted, substituted,and/or heteroatom-containing alkylene and lower alkylene, respectively.

The term “alicyclic” is used to refer to cyclic, non-aromatic compounds,substituents and linkages, e.g., cycloalkanes and cycloalkenes,cycloalkyl and cycloalkenyl substituents, and cycloalkylene andcycloalkenylene linkages. Often, the term refers to polycycliccompounds, substituents, and linkages, including bridged bicyclic,compounds, substituents, and linkages. Preferred alicyclic moietiesherein contain in the range of 3 to about 30 carbon atoms, typically 3to about 18 carbon atoms, and more typically 5 to about 14 carbon atoms.Unless otherwise indicated, the term “alicyclic” includes substitutedand/or heteroatom-containing such moieties. It will be appreciated thatthe term “cyclic,” as used herein, thus includes “alicyclic” moieties.

The term “fluorinated” refers to replacement of a hydrogen atom in amolecule or molecular segment with a fluorine atom, and includesperfluorinated moieties. The term “perfluorinated” is also used in itsconventional sense to refer to a molecule or molecular segment whereinall hydrogen atoms are replaced with fluorine atoms, while the term“semi-fluorinated” refers to a molecule or molecular segment whereinfewer than all hydrogen atoms are replaced with fluorine atoms. Thus, a“fluorinated” methyl group encompasses —-CH₂F and —CHF₂ as well as the“perfluorinated” methyl group, i.e., —CF₃ (trifluoromethyl).

The term “fluoroalkanol” as used herein refers to a compound orsubstituent containing a fluorinated, hydroxyl-substituted alkyl group,with “alkyl” defined as above. Fluoroalkanols and fluoroalcoholsubstituents may be semi-fluorinated or perfluorinated.

The term “heteroatom-containing” as in a “heteroatom-containing alkylgroup” (also termed a “heteroalkyl” group) refers to a molecule, linkageor substituent in which one or more carbon atoms are replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Examples of heteroalkylgroups include alkoxyalkyl, alkoxyaryl, alkylthio-substituted alkyl, andthe like.

Unless otherwise indicated, the term “hydrocarbyl” is to be interpretedas including substituted and/or heteroatom-containing hydrocarbylmoieties. “Hydrocarbyl” refers to univalent hydrocarbyl radicalscontaining 1 to about 30 carbon atoms, preferably 1 to about 18 carbonatoms, most preferably 1 to about 12 carbon atoms, including linear,branched, cyclic, alicyclic, and aromatic species. “Substitutedhydrocarbyl” refers to hydrocarbyl substituted with one or moresubstituent groups, and the terms “heteroatom-containing hydrocarbyl”and “heterohydrocarbyl” refer to hydrocarbyl in which at least onecarbon atom is replaced with a heteroatom.

The term “polyol” refers to an organic compound containing two or morehydroxyl groups.

By “substituted” as in “substituted alkyl,” “substituted alkylene,” andthe like, as alluded to in some of the aforementioned definitions, it ismeant that in the alkyl, alkylene, or other moiety, at least onehydrogen atom bound to a carbon (or other) atom is replaced with anon-hydrogen substituent. Examples of such substituents include, withoutlimitation, functional groups such as halide, hydroxyl, sulfhydryl,alkoxy, and acyl (including alkylcarbonyl (—CO-alkyl)), and hydrocarbylmoieties such as alkyl, including linear, branched, and cyclic alkyl.The functional groups may, if a particular group permits, be furthersubstituted with one or more additional functional groups or with one ormore hydrocarbyl moieties such as those specifically enumerated, andanalogously, a hydrocarbyl substituent may be further substituted withone or more functional groups or additional hydrocarbyl moieties such asthose specifically enumerated.

When two substituents are indicated as being “taken together to form aring,” several possibilities are encompassed. That is, when R and R′ ofthe following hypothetical compound are indicated as being takentogether to form a ring

the resulting compounds include (1) those wherein a single spacer atomlinks the carbon atoms indicated at * and ** (i.e., R and R′ “takentogether” together form a single atom that may or may not besubstituted, e.g., CH₂ or O), (2) those wherein a direct covalent bondis formed between R and R′, and (3) those wherein R and R′ are linkedthrough a bifunctional moiety containing one or more spacer atoms. Inaddition, compounds in which R and R′ are “taken together to form aring” include compounds in which the linked atoms are not necessarilycontained within a terminal group. For example, when R of the aboveformula is —CH₂CH₃ and R′ is —CH₂CF₃, such that the compound has thestructure

then compounds in which R and R′ are taken together to form a ringinclude both

The term “ring” is intended to include all types of cyclic groups,although the rings of primary interest herein are alicyclic, includingcycloalkyl and substituted and/or heteroatom-containing cycloalkyl,whether monocyclic, bicyclic (including bridged bicyclic), orpolycyclic. Preferred rings are substituted and/or heteroatom-containingmonocyclic rings.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

II. Alkene Fluoroalkanols and Synthesis Thereof

In one aspect of the invention, novel alkene fluoroalkanols areprovided, as is a method is provided for synthesizing an alkenefluoroalkanol. The alkene fluoroalkanols of the invention, which arealkenes containing a fluorinated hydroxyalkyl group, are particularlyuseful as starting materials in the synthesis of polymerizable olefinmonomers via unsaturated fluoroalkanol intermediates. The alkenefluoroalkanols have the structure of formula (III)

wherein the substituents indicated are as follows:

R¹ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl(e.g., fluorinated C₁-C₂₄ alkyl), C₁-C₂₄ alkoxy, and substituted C₁-C₂₄alkoxy (e.g., fluorinated C₁-C₂₄ alkoxy). Preferred R¹ moieties include,without limitation, hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ hydroxyalkyl,fluorinated C₁-C₁₂ alkyl, fluorinated C₃-C₁₂ hydroxyalkyl, fluorinatedC₃-C₁₂ alkyl substituted with a protected hydroxyl group, and C₁-C₁₂alkoxy, while more preferred R¹ moieties are hydrogen, C₁-C₈ alkyl,C₁-C₈ alkoxy, and fluorinated hydroxyalkyl having the structure-(L¹)_(n1)-CR⁸R⁹—OH in which n1 is zero or 1, L¹ is C₁-C₆ aliphatic, R⁸is selected from hydrogen, C₁-C₈ alkyl, and fluorinated C₁-C₈ alkyl, andR⁹ is fluorinated C₁-C₈ alkyl. Optimally, R¹ is selected from hydrogen,C₁-C₄ alkyl, C₁-C₄ alkoxy, and -(L¹)_(n1)-CR⁸R⁹—OH in which n1 is zeroor 1, L¹ is C₁-C₄ aliphatic, R⁸ is selected from hydrogen, methyl,trifluoromethyl, difluoromethyl, and fluoromethyl, and R⁹ is selectedfrom methyl, trifluoromethyl, difluoromethyl, and fluoromethyl. Forexample, R¹ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl,methoxy, ethoxy, 2-methoxy-propyl, —CH(CF₃)—OH, —C(CH₃)(CF₃)—OH,—C(CF₃)(CF₃)—OH, —CH(CHF₂)—OH, —C(CH₃)(CHF₂)—OH, —C(CF₃)(CHF₂)—OH,—CH(CH₂F)—OH, —C(CH₃)(CH₂F)—OH, —C(CF₃)(CH₂F)—OH, —C(CF₂H)(CH₂F)—OH,—CH₂—CH(CF₃)—OH, —CH₂—C(CH₃)(CF₃)—OH, —CH₂—C(CF₃)₂—OH, —CH₂—CH(CHF₂)—OH,—CH₂—C(CH₃)(CHF₂)—OH, —CH₂—C(CHF₂)₂—OH, —CH₂—CH(CH₂F)—OH,—CH₂—C(CH₃)(CH₂F)—OH, —CH₂—C(CH₂F)₂—OH, —CF₂—CH(CF₃)—OH,—CF₂—C(CH₃)(CF₃)—OH, —CF₂—C(CF₃)₂—OH, —CF₂—CH(CHF₂)—OH,—CF₂—C(CH₃)(CHF₂)—OH, —CF₂—C(CHF₂)₂—OH, —CF₂—CH(CH₂F)—OH,—CF₂—C(CH₃)(CH₂F)—OH, or —CF₂—C(CH₂F)₂—OH.

R² is selected from hydrogen, C₁-C₂₄ alkyl and substituted C₁-C₂₄ alkyl(e.g., fluorinated C₁-C₂₄ alkyl), and is preferably hydrogen, C₁-C₁₂alkyl, or substituted C₁-C₁₂ alkyl, particularly fluorinated C₁-C₁₂alkyl. More preferably, R² is hydrogen or C₁-C₈ alkyl, and, mostpreferably, R² is hydrogen or C₁-C₄ alkyl, e.g., methyl, ethyl,n-propyl, isopropyl, n-butyl, or the like.

R³, R⁴, and R⁵ are independently selected from hydrogen, C₁-C₂₄ alkyl,and substituted C₁-C₂₄ alkyl, and are preferably selected from C₁-C₁₂alkyl, C₁-C₁₂ hydroxyalkyl, fluorinated C₁-C₁₂ alkyl, fluorinated C₁-C₁₂hydroxyalkyl, and fluorinated C₁-C₁₂ alkyl substituted with a protectedhydroxyl group. Typically, R³, R⁴, and R⁵ are selected from hydrogen,C₁-C₈ alkyl, and fluorinated hydroxyalkyl having the structure-(L²)_(n2)-CR^(8A)R^(9A)—OH in which: n2 is zero or 1; L² is C₁-C₆aliphatic, preferably C₁-C₄ aliphatic; R^(8A) is selected from hydrogen,C₁-C₈ alkyl, and fluorinated C₁-C₈ alkyl; and R^(9A) is fluorinatedC₁-C₈ alkyl. For example, R^(8A) may be hydrogen, methyl,trifluoromethyl, difluoromethyl, or fluoromethyl, and R^(9A) may bemethyl, trifluoromethyl, difluoromethyl, or fluoromethyl.

It should also be noted that any two of R¹, R², R³, R⁴, and R⁵ may betaken together to form a ring, generally a C₃-C₃₀ alicyclic group,preferably a C₃-C₁₈ alicyclic group, and typically a C₅-C₁₄ alicyclicgroup. Such alicyclic groups include substituted alicyclic groups,particularly fluorinated alicyclic groups. Examples of alicyclic groupsthat may be formed by two of R¹, R², R³, R⁴, and R⁵ include, withoutlimitation, cyclopentyl, cyclohexyl, adamantyl, norbornyl, andsubstituted analogs thereof.

R^(6A) and R^(7A) are substituents within the fluoroalkanol group—(CR^(6A)R^(7A)—OH, and, accordingly, at least one of R^(6A) and R^(7A)is fluorinated. In general, R^(6A) is selected from hydrogen, C₁-C₂₄alkyl, substituted C₁-C₂₄ alkyl, and —(CO)—R in which R is hydrogen,hydroxyl, halo, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl (includingfluorinated C₁-C₂₄ alkyl), amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino, and R^(7A) is C₁-C₂₄ alkyl or substituted C₁-C₂₄ alkyl(including fluorinated C₁-C₂₄ alkyl). More typically, R^(6A) is selectedfrom hydrogen, C₁-C₁₂ alkyl, and C₁-C₁₂ haloalkyl, and R^(7A) is C₁-C₁₂alkyl or fluorinated C₁-C₁₂ alkyl. In a preferred embodiment, R^(6A) isselected from hydrogen, C₁-C₈ alkyl, and fluorinated C₁-C₈ alkyl; andR^(7A) is C₁-C₈ alkyl or fluorinated C₁-C₈ alkyl. Optimally, R^(6A) isselected from hydrogen, C₁-C₄ alkyl, semi-fluorinated C₁-C₄ alkyl, andperfluorinated C₁-C₄ alkyl, and R^(7A) is selected from C₁-C₄ alkylsemi-fluorinated C₁-C₄ alkyl, and perfluorinated C₁-C₄ alkyl. Exemplary—CR^(6A)R^(7A)—OH groups thus include —CH(CF₃)—OH, —C(CH₃)(CF₃)—OH,—C(CF₃)(CF₃)—OH, —CH(CHF₂)—OH, —C(CH₃)(CHF₂)—OH, —C(CF₃)(CHF₂)—OH,—CH(CH₂F)—OH, —C(CH₃)(CH₂F)—OH, —C(CF₃)(CH₂F)—OH, and —C(CF₂H)(CH₂F)—OH.Particularly preferred —CR^(6A)R^(7A)—OH moieties are those whereinR^(6A) and R^(7A) are both trifluoromethyl and those wherein one ofR^(6A) and R^(7A) is methyl and the other is trifluoromethyl, i.e.,—C(CH₃)(CF₃)—OH and —C(CF₃)(CF₃)—OH. In addition, R^(6A) and R^(7A) maybe taken together to form a ring, e.g., a fluorinated alicyclic group,of C₃-C₃₀, preferably C₃-C₁₈, and most preferably C₅-C₁₄ carbon atoms.The alicyclic group may be unsubstituted or substituted, e.g., with oneor more fluorine atoms.

Representative alkene fluoroalkanols of the invention include, but arenot limited to, the following specific compounds:

The alkene fluoroalkanols of the invention are synthesized in astraightforward, single step reaction. The reaction involves contactingan olefinic reactant directly substituted on an olefinic carbon atomwith a substituted or unsubstituted methyl group with a fluorinatedcarbonyl compound under reaction conditions and for a time periodeffective to allow addition of the olefinic reactant to the carbonylcarbon of the fluorinated carbonyl compound. The fluorinated carbonylcompound may be symmetrically or asymmetrically substituted, and in oneembodiment excludes hexafluoroacetone. The reaction is illustrated inScheme 1:

In reactant (I), R¹, R², R³, R⁴, and R⁵ are as defined previously, andit will be appreciated that the substituted or unsubstituted methylgroup is the —CR¹R² moiety shown within the structure. In reactant (II),R⁶ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl(e.g., fluorinated C₁-C₂₄ alkyl), C₃-C₂₅ acylmethyl, (fluorinated C₂-C₂₄acyl)-substituted methyl, (fluorinated C₂-C₂₄ acyl)-substituteddifluoromethyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo,C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, ordi(C₁-C₂₄ alkyl)amino, and R⁷ is C₁-C₂₄ alkyl or fluorinated C₁-C₂₄alkyl, with the proviso that at least one of R⁶ and R⁷ is fluorinated.However, R⁶ is generally selected from hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂haloalkyl, C₃-C₁₃ acylmethyl, (fluorinated C₂-C₁₂ acyl)-substitutedmethyl, and (fluorinated C₂-C₁₂ acyl)-substituted difluoromethyl, whileR⁷ is generally C₁-C₁₂ alkyl or fluorinated C₁-C₁₂ alkyl. Preferably, R⁶is selected from hydrogen, C₁-C₈ alkyl, fluorinated C₁-C₈ alkyl, C₃-C₉acylmethyl, (fluorinated C₂-C₈ acyl)-substituted methyl, and(fluorinated C₂-C₈ acyl)-substituted difluoromethyl, and R⁷ is C₁-C₈alkyl or fluorinated C₁-C₈ alkyl. Optimally, R⁶ is selected fromhydrogen, C₁-C₄ alkyl, semi-fluorinated C₁-C₄ alkyl, perfluorinatedC₁-C₄ alkyl, and R¹²—(CO)—CR¹⁰R¹¹— in which R¹⁰ and R¹¹ are H or F andR¹² is methyl or trifluoromethyl, and R⁷ is selected from C₁-C₄ alkyl,semi-fluorinated C₁-C₄ alkyl, and perfluorinated C₁-C₄ alkyl. In theproduct (III), R¹, R², R³, R⁴, R⁵, R^(6A), and R^(7A) are as definedpreviously.

With certain fluorinated carbonyl compounds of formula (II), i.e., thosecontaining a R¹²—(CO)—CR¹⁰R¹¹— substituent at R⁶, cyclic alkenefluoroalkanols result as shown in Scheme 2 (for simplicity, R⁴ and R⁵ ofthe olefinic reactant (I) are H and therefore not shown):

As indicated in the scheme, the cyclic alkene fluoroalkanols can then beconverted to cyclic polyols, as will be described infra.

In addition, alkene fluoroalkanols substituted with two or morefluoroalkanol groups can be synthesized by using an excess of thefluorinated carbonyl reagent (II), such that two or more fluoroalkanolgroups become incorporated into the compound. Such a reaction isillustrated in Scheme 3:

The reactions illustrated in Schemes 1, 2, and 3 are carried out at atemperature typically in the range of about −20° C. to about 20° C.After 2-12 hours, the temperature is raised, and the product maythereafter be isolated and optionally purified using any suitable means.A specific synthesis of an alkene fluoroalkanol is described in Example1.

III. Fluorinated Polyols Synthesized from the Alkene Fluoroalkanols

The alkene fluoroalkanols of formula (III) are useful as precursors tosaturated fluorinated polyols which, in turn, can be converted topolymerizable olefins as will be described infra. In one embodiment, thefluorinated polyols have the structure of formula (IV)

wherein R¹, R², R³, R⁴, R⁵, R^(6A), and R^(7A) are as defined previouslyfor the alkene fluoroalkanols of formula (III), and one of R¹³ and R¹⁴is hydroxyl and the other is selected from hydrogen and hydroxyl, and isusually hydrogen.

In a preferred fluorinated polyol of formula (IV):

R¹ is selected from hydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, and-(L¹)_(n1)-CR⁸R⁹—OH in which n1 is zero or 1, L¹ is C₁-C₄ aliphatic, R⁸is selected from hydrogen, methyl, trifluoromethyl, difluoromethyl, andfluoromethyl, and R⁹ is selected from methyl, trifluoromethyl,difluoromethyl, and fluoromethyl;

R² is hydrogen or C₁-C₄ alkyl;

R³, R⁴, and R⁵ are independently selected from hydrogen, C₁-C₄ alkyl,and -(L²)_(n2)-CR^(8A)R^(9A)—OH in which n2 is zero or 1, L² is C₁-C₄aliphatic, R^(8A) is selected from hydrogen, methyl, trifluoromethyl,difluoromethyl, and fluoromethyl, and R^(9A) is selected from methyl,trifluoromethyl, difluoromethyl, and fluoromethyl, and further whereinany two of R¹, R³, R⁴, and R⁵ may be taken together to form a C₅-C₁₄alicyclic group;

R^(6A) is selected from hydrogen, C₁-C₄ alkyl, semi-fluorinated C₁-C₄alkyl, and perfluorinated C₁-C₄ alkyl, and is optimally methyl ortrifluoromethyl; and

R^(7A) is selected from C₁-C₄ alkyl, semi-fluorinated C₁-C₄ alkyl, andperfluorinated C₁-C₄ alkyl, and is optimally trifluoromethyl.

In the most preferred embodiment, R² and R³ are taken together to form aC₃-C₃₀ alicyclic group, preferably a C₃-C₁₈ alicyclic group, mostpreferably a C₅-C₁₄ alicyclic group, and R⁴ and R⁵ are hydrogen.

Representative fluorinated polyols of the invention include, but are notlimited to, the following specific compounds:

The fluorinated polyol is readily synthesized from the alkenefluoroalkanol using a hydroboration reaction, in which an alkenefluoroalkanol having the structure of formula (III) is contacted with asubstituted or unsubstituted borane, followed by addition of aqueousbase and hydrogen peroxide, preferably in that order, to the reactionmixture. Examples of suitable boranes are those having the structureBHR⁵⁴R⁵⁵ in which R⁵⁴ and R⁵⁵ are independently selected from hydrogen,halo, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl, C₁-C₂₄ alkoxy, substitutedC₁-C₂₄ alkoxy, or wherein R⁵⁴ and R⁵⁵ may be taken together to form analicyclic group. Preferably, R⁵⁴ and R⁵⁵ are independently selected fromhydrogen, chloro, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy,and substituted C₁-C₁₂ alkoxy. The reaction proceeds according to Scheme4:

Examples 2, 3, and 9-12 describe specific reactions in which fluorinatedpolyols of the invention are synthesized.

IV. Fluoroalkanol-Substituted α,β-Unsaturated Esters

The fluorinated polyols described in part (III) of this section arereadily converted to polymerizable olefins in the form offluoroalkanol-substituted α,β-unsaturated esters, i.e.,fluoroalkanol-substituted acrylates, methacrylates, and analogs thereof.In one embodiment, then, the invention provides afluoroalkanol-substituted α,β-unsaturated ester having the structure offormula (V)

wherein:

R¹ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl,C₁-C₂₄ alkoxy, and substituted C₁-C₂₄ alkoxy;

R², R³, R⁴, and R⁵ are independently selected from hydrogen, C₁-C₂₄alkyl, and substituted C₁-C₂₄ alkyl, and further wherein any two of R¹,R², R³, R⁴, and R⁵ may be taken together to form a ring;

R^(6A) is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C₁-C₂₄ alkyl,substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino;

R^(7A) is C₁-C₂₄ alkyl or substituted C₁-C₂₄ alkyl, and further whereinR^(6A) and R^(7A) may be taken together to form a ring, with the provisothat at least one of R^(6A) and R^(7A) is fluorinated; and

one of R¹⁵ and R¹⁶ is hydrogen, and the other has the structure offormula (VI)

in which R¹⁷ is selected from hydrogen, fluoro, C₁-C₄ alkyl, fluorinatedC₁-C₄ alkyl, —CH₂—COOH, —CF₂—COOH, —CH₂—COOR²⁰, and —CF₂—COOR²⁰, R¹⁸ ishydrogen or fluoro, R¹⁹ is hydrogen, fluoro, or —COOH, and R²⁰ is anonhydrogen substituent.

In preferred compounds of formula (VI), the R¹, R², R³, R⁴, R⁵, R^(6A),and R^(7A) substituents are defined as for preferred compounds offormulas (III) and (IV), and:

R¹⁷ is selected from hydrogen, fluoro, methyl, trifluoromethyl,—CH₂—COOH, and —CH₂—COOR²⁰;

R¹⁸ and R¹⁹ are independently selected from hydrogen and fluoro; and

R²⁰ is selected from C₁-C₁₂ alkyl and substituted C₁-C₁₂ alkyl.

In particularly preferred compounds of formula (V), R¹⁷ is selected fromhydrogen and methyl, and R¹⁹ are hydrogen.

In a related embodiment, the invention provides afluoroalkanol-substituted α,β-unsaturated ester having the structure offormula (VII)

wherein the substituents are as follows:

R²¹ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl(e.g., fluorinated C₁-C₂₄ alkyl), C₁-C₂₄ alkoxy, and substituted C₁-C₂₄alkoxy (e.g., fluorinated C₁-C₂₄ alkoxy). Preferred R²¹ moietiesinclude, without limitation, hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂hydroxyalkyl, fluorinated C₁-C₁₂ alkyl, fluorinated C₃-C₁₂ hydroxyalkyl,fluorinated C₃-C₁₂ alkyl substituted with a protected hydroxyl group,and C₁-C₁₂ alkoxy, while more preferred R²¹ moieties are hydrogen, C₁-C₈alkyl, C₁-C₈ alkoxy, and fluorinated hydroxyalkyl having the structure-(L¹)_(n1)-CR⁸R⁹—OH in which n1, L¹, R⁸, R⁹ are as defined earlierherein. In a most preferred embodiment, R²¹ is selected from hydrogen,C₁-C₄ alkyl, C₁-C₄ alkoxy, and -(L¹)_(n1)-CR⁸R⁹—OH in which n1 is zeroor 1, L¹ is C₁-C₄ aliphatic, R⁸ is selected from hydrogen, methyl,trifluoromethyl, difluoromethyl, and fluoromethyl, and R⁹ is selectedfrom methyl, trifluoromethyl, difluoromethyl, and fluoromethyl. Forexample, R¹ may be methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl,methoxy, ethoxy, 2-methoxy-propyl, —CH(CF₃)—OH, —C(CH₃)(CF₃)—OH,—C(CF₃)(CF₃)—OH, or the like.

R²² is selected from hydrogen, C₁-C₂₄ alkyl, and substituted C₁-C₂₄alkyl (e.g., fluorinated C₁-C₂₄ alkyl), and is preferably hydrogen,C₁-C₁₂ alkyl, or substituted C₁-C₁₂ alkyl, particularly fluorinatedC₁-C₁₂ alkyl. More preferably, R²² is hydrogen or C₁-C₈ alkyl, and, mostpreferably, R²² is hydrogen or C₁-C₄ alkyl, e.g., methyl, ethyl,n-propyl, isopropyl, n-butyl, or the like.

One of R²³ and R²⁶ is hydrogen, and the other has the structure offormula (VI)

wherein R¹⁷, R¹⁸, and R¹⁹ are defined as for the fluorinated esters offormula (V). In representative compounds of formula (VII), R²³ and R²⁶are both trifluoromethyl, or one of R²³ and R²⁶ is methyl and the otheris trifluoromethyl.

R²⁴ and R²⁵ are selected from hydrogen, C₁-C₂₄ alkyl and substitutedC₁-C₂₄ alkyl, or may be taken together to form a ring. Generally, R²⁴and R²⁵ are selected from hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ hydroxyalkyl,fluorinated C₁-C₁₂ alkyl, fluorinated C₁-C₁₂ hydroxyalkyl, fluorinatedC₁-C₁₂ alkyl substituted with a protected hydroxyl group, and C₁-C₁₂alkoxy, or may be taken together to form a C₃-C₃₀ alicyclic group;preferably, R²⁴ and R²⁵ are independently selected from hydrogen, C₁-C₈alkyl, and fluorinated hydroxyalkyl having the structure-(L²)_(n2)-CR^(8A)R^(9A)—OH in which n2, L², R^(8A), and R^(9A) are asdefined earlier herein.

R²⁷ is selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄ alkyl,and —(CO)—R in which R is hydrogen, hydroxyl, halo, C₁-C₂₄ alkyl,substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino, and R³⁰ is C₁-C₂₄ alkyl or substituted C₁-C₂₄ alkyl, withthe proviso that at least one of R²⁷ and R³⁰ is fluorinated. Preferably,R²⁷ is hydrogen, C₁-C₁₂ alkyl, and C₁-C₁₂ haloalkyl, and R³⁰ is C₁-C₁₂alkyl or fluorinated C₁-C₁₂ alkyl. In a more preferred embodiment, R²⁷is selected from hydrogen, C₁-C₈ alkyl, and fluorinated C₁-C₈ alkyl, andR³⁰ is C₁-C₈ alkyl or fluorinated C₁-C₈ alkyl. Optimally, R²⁷ isselected from hydrogen, C₁-C₄ alkyl, semi-fluorinated C₁-C₄ alkyl, andperfluorinated C₁-C₄ alkyl, and R³⁰ is selected from C₁-C₄ alkyl,semi-fluorinated C₁-C₄ alkyl, and perfluorinated C₁-C₄ alkyl.

R²⁸ and R²⁹ are independently selected from hydrogen, fluoro, C₁-C₂₄alkyl, and substituted C₁-C₂₄ alkyl, or may be taken together to form aring, and are preferably selected from hydrogen, fluoro, C₁-C₁₂ alkyl,and substituted C₁-C₁₂ alkyl.

It will be appreciated that the fluorinated polyol precursor used tosynthesize the aforementioned ester has the structure of formula (VIIA)

wherein the R substituents are as defined for esters of formula (VII)except with respect to R^(23A) and R^(26A): that is, one of R^(23A) andR^(26A) is hydrogen and the other is hydroxyl.

In a further embodiment, a the invention provides afluoroalkanol-substituted α,β-unsaturated ester having the structure offormula (VIII):

wherein:

R³¹ and R³² are defined as for R^(6A) and R^(7A), i.e., R³¹ and R³² areindependently selected from hydrogen, C₁-C₂₄ alkyl, substituted C₁-C₂₄alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C₁-C₂₄ alkyl,substituted C₁-C₂₄ alkyl, amino, C₁-C₂₄ alkylamino, or di(C₁-C₂₄alkyl)amino, with the proviso that at least one of R³¹ and R³² isfluorinated, and further wherein R³¹ and R³² may be taken together toform a fluorinated alicyclic group. Preferred R³¹ and R³² moietiescorrespond to the preferred R^(6A) and R^(7A) moieties described withrespect to the alkene fluoroalkanols of formula (III).

R³⁹ and R⁴⁰ are defined as for R³¹ and R³², respectively.

R³³, R³⁴, R³⁵, R³⁶, R³⁷, and R³⁸ are selected from hydrogen, C₁-C₂₄alkyl, and substituted C₁-C₂₄ alkyl, and further wherein any two of R³³,R³⁴, R³⁵, R³⁶, R³⁷, and R³⁸ may be taken together to form a ring, withthe proviso that one of R³⁶ and R³⁷ is hydrogen, and the other has thestructure of formula (VI)

wherein R¹⁷, R¹⁸, and R¹⁹ are as defined earlier herein. Preferred R³³,R³⁴, R³⁵, and R³⁸ substituents are defined as for R⁴ and R⁵ in thefluoroalkanol-substituted α,β-unsaturated esters of formula (V), whilepreferred R³⁶ and R³⁷ substituents are defined as for R¹⁵ and R¹⁶ in theesters of formula (V).

Again, it will be appreciated that the fluorinated polyol precursor usedto synthesize the aforementioned ester has the structure of formula(VIIIA)

wherein the R substituents are as defined for esters of formula (VIII)except with respect to R^(36A) and R^(37A), one of which is hydrogen andthe other of which is hydroxyl.

In a further embodiment, a fluoroalkanol-substituted α,β-unsaturatedester is provided having the structure of formula (IX)

wherein:

R⁴¹, R⁴², R⁴⁸, R⁴⁹, R⁵², and R⁵³ are defined as for R³¹, R³², R³⁹, andR⁴⁰; and

R⁴³, R⁴⁴, R⁴⁶, R⁴⁷, R⁵⁰, and R⁵¹ are defined as for R³³, R³⁴, R³⁵, R³⁶,R³⁷, and R³⁸, wherein any two of R⁴³, R⁴⁴, R⁴⁶, R⁴⁷, R⁵⁰, and R⁵¹ may betaken together to form an alicyclic group, with the proviso that one ofR⁴⁵ and R⁴⁶ is hydrogen, and the other has the structure of formula (VI)

wherein R¹⁷, R¹⁸, and R¹⁹ are as defined earlier herein. Preferred R⁴³,R⁴⁴, R⁴⁶, R⁴⁷, R⁵⁰, and R⁵¹ substituents are defined as for R⁴ and R⁵ inthe fluoroalkanol-substituted α,β-unsaturated esters of formula (V),while preferred R45 and R⁴⁶ substituents are defined as for R¹⁵ and R¹⁶in the esters of formula (V).

The corresponding polyol precursor has the structure of formula (IXA)

wherein the R substituents are as defined for esters of formula (IX)except with respect to R^(45A) and R^(46A), one of which is hydrogen andthe other of which is hydroxyl.

Representative fluoroalkanol-substituted α,β-unsaturated esters of theinvention include, but are not limited to, the following specificacrylates and methacrylates:

These fluoroalkanol-substituted α,β-unsaturated esters are synthesizedfrom a fluorinated polyol as provided herein by contacting thefluorinated polyol with an acylation reagent selected from acylchlorides of the formula Cl—(CO)—CR¹⁷═CR¹⁸R¹⁹ and anhydrides of theformula O[(CO)—CR¹⁷═CR¹⁸R¹⁹]₂, under reaction conditions effective toresult in esterification of a hydroxyl group other than that present inthe fluoroalkanol moiety or moieties. For instance, esterification ofthe fluorinated polyol of formula (V) proceeds according to Scheme 5.

In the acylation reagents, R¹⁷ is selected from hydrogen, fluoro, C₁-C₄alkyl, fluorinated C₁-C₄ alkyl, —CH₂—COOH, —CF₂—COOH, —CH₂—COOR²⁰, and—CF₂—COOR²⁰, R¹⁸ is hydrogen or fluoro, R¹⁹ is hydrogen, fluoro, or—COOH, and R²⁰ is a nonhydrogen substituent.

In a preferred embodiment, the fluorinated polyol is treating with adeprotonating base prior to reaction with the acylation reagent.

Examples 4-8 describe acylation reactions in which fluorinated polyolsare converted to fluoroalkanol-substituted α,β-unsaturated esters of theinvention.

It will be appreciated that cyclic fluoroalkanol-substitutedα,β-unsaturated esters such as those of formula (VII), as well ascomplex fluoroalkanol-substituted α,β-unsaturated esters such as thoseof formulae (VIII) and (IX), result from initially using a fluorinatedcarbonyl compound (II) in which an additional carbonyl compound ispresent. Such fluorinated carbonyl compounds include, withoutlimitation, compounds of formula (II) in which R⁶ is selected fromC₃-C₂₅ acylmethyl, (fluorinated C₂-C₂₄ acyl)-substituted methyl, and(fluorinated C₂-C₂₄ acyl)-substituted difluoromethyl, particularlyC₃-C₁₃ acylmethyl, (fluorinated C₂-C₁₂ acyl)-substituted methyl, and(fluorinated C₂-C₁₂ acyl)-substituted difluoromethyl, preferably C₃-C₉acylmethyl, (fluorinated C₂-C₈ acyl)-substituted methyl, and(fluorinated C₂-C₈ acyl)-substituted difluoromethyl. Specific suchcompounds are those having the structure R¹²—(CO)—CR¹⁰R¹¹—(CO)—R⁷,wherein R¹⁰ and R¹¹ are H or F, R¹² is methyl or trifluoromethyl, and R⁷is selected from C₁-C₄ alkyl, semi-fluorinated C₁-C₄ alkyl, andperfluorinated C₁-C₄ alkyl. Representative such reactions are shown inSchemes 2 and 3.

The fluoroalkanol-substituted α,β-unsaturated esters can be polymerizedto provide a fluoroalkanol-substituted polymer using any effectivepolymerization process, e.g., radical polymerization using a suitablefree radical initiator such as benzoyl peroxide (BPO) orazobisisobutyronitrile (AIBN). For instance, the monomers can bedissolved in an appropriate solvent that, at reflux, will afford amedium that maintains a constant temperature suitable for activation ofthe initiator without inducing side reactions involving functionalgroups of the monomers. The solution can be prepared so as to afford arelatively high concentration of monomer, for example 30 wt %. Theinitiator is then added and the solution is degassed by bubbling withdry nitrogen. The reaction flask is then immersed in preheated oil bathand allowed to reflux for several hours. After cooling the solution toroom temperature, the polymer is isolated by precipitation into anexcess volume, for example twenty-fold, of an appropriate nonsolvent.The polymer is isolated by filtration, washed with the nonsolvent anddried to constant weight under vacuum. Polymers prepared using thefluoroalkanol-substituted α,β-unsaturated esters of the invention areuseful in the manufacture of lithographic photoresist compositions.

It is to be understood that while the invention has been described inconjunction with the preferred specific embodiments thereof, that theforegoing description as well as the examples that follow are intendedto illustrate and not limit the scope of the invention. Other aspects,advantages and modifications within the scope of the invention will beapparent to those skilled in the art to which the invention pertains.

All patents, patent applications, and publications mentioned herein arehereby incorporated by reference in their entireties.

EXAMPLE 1 1,1,1-Trifluoro-2-trifluoromethyl-4-methyl-pent-4-en-2-ol (1)

Hexafluoroacetone (238 g) and 120 g of isobutylene were condensed into alecture bottle using Dry Ice/2-propanol cooling. The temperature wasraised in the sealed vessel to 20° C. while stirring in a water bath andtemperature maintained overnight. The next morning the temperature wasraised to 50° C. for 2 hours. After cooling, excess isobutylene was bledoff and the product distilled at 100-115° C. to afford 264 g (83%) of aclear liquid. The identity of the product was confirmed using ¹H NMRspectroscopy and HRMS.

EXAMPLE 2 Synthesis of1,1,1-trifluoro-2-trifluoromethyl-4-methyl-2,5-pentanediol (2)

To a 3-necked, 500 mL round bottomed flask equipped with an overheadstirrer, digital thermometer and a 125 mL constant-pressure additionfunnel with a nitrogen inlet was added 27 mL (0.27 mol) ofborane-dimethylsulfide complex (10.0M in THF). The addition funnel wascharged with a solution of 50 g (0.23 mol) of1,1,1-trifluoro-2-trifluoromethyl-4-methylpent-4-en-2-ol (1) in 140 mLof anhydrous THF. The flask was cooled and the olefin was added slowlywith stirring while maintaining a temperature below 15° C. The mixturewas stirred at room temperature overnight after which time it wasrecooled and 100 mL (0.3 mol) of 3M NaOH (aq) was added carefully. Thereaction mixture was reduced in volume on a rotary evaporator andsubsequently co-evaporated with two 500 mL portions of diethyl ether.The resulting heavy oil was taken up in 50 mL of THF and the solutiontransferred to a 250 mL 3-necked round bottomed flask equipped with a125-mL addition funnel, a digital thermometer, and a magnetic stirbar.The addition funnel was charged with 70 mL of 30% hydrogen peroxide. Theflask was cooled and the hydrogen peroxide added slowly with stirring.After stirring overnight at room temperature, the solution was dilutedwith 500 mL of diethyl ether and adjusted to pH 6 (wet litmus) with 5%HCl. The ether layer was separated and the aqueous layer was extractedwith 2×250 mL of ether. The combined organic phases were washed with2×500 mL of saturated ammonium chloride and brine, dried over MgSO₄, andevaporated to a yellow oil. The oil was purified by distillation througha Vigreux column, bp 57° C.@1.0 mm Hg to yield 46 g (85%) of (2) as alow melting solid. The identity of the product was confirmed using ¹HNMR spectroscopy and HRMS.

EXAMPLE 3 1,1,1-Trifluoro-2-trifluoromethyl-2,5-pentanediol (4) and1,1,1-trifluoro-2-trifluoromethyl-2,4-pentanediol (5)

To a 3-necked, 3-L round bottomed flask equipped with an overheadstirrer, digital thermometer and a 1-L constant-pressure addition funnelwith a nitrogen inlet was added 974 mL (1.95 mol) ofborane-dimethylsulfide complex (2.0 M in THF). The addition funnel wascharged with a solution of 353 g (1.7 mol) of1,1,1-trifluoro-2-trifluoromethyl-pent-4-en-2-ol (3) (synthesized as inExample 1 from hexafluoroacetone and propene) in 400 mL of anhydrousTHF. The flask was cooled and the olefin was added slowly with stirringwhile maintaining a temperature below 15° C. The mixture was stirred atroom temperature for two days after which time it was recooled and 750mL (2.25 mol) of 3 M NaOH (aq) was added carefully. The reaction mixturewas reduced in volume on a rotary evaporator and subsequentlyco-evaporated with two 500 mL portions of diethyl ether. The resultingheavy oil was taken up in 300 mL of THF and the solution transferred toa 1-L 3-necked round-bottomed flask equipped with a 250-mL additionfunnel, a digital thermometer, and a magnetic stir bar. The additionfunnel was charged with 250 mL of 30% hydrogen peroxide. The flask wascooled and the hydrogen peroxide added slowly with stirring. Afterstirring overnight at room temperature, the solution was diluted with 1L of diethyl ether and adjusted to pH 6 (wet litmus) with 5% HCl. Theether layer was separated and the aqueous layer was extracted with 2×500mL of ether. The combined organic phases were washed with 2×500 mL ofsaturated ammonium chloride and brine, dried over MgSO₄ and evaporatedto a crude yield of 379 g of a 45:55 (2°:1°) mixture of the two titlealcohols. The diols were separated by distillation through a 12″Vigreux, bp 47° C. at 1.0 mm Hg (2° alcohol) and bp 55° C. at 1.0 mm Hg(1° alcohol). The 1° alcohol (4) is a viscous oil while the 2° alcohol(5) is a low melting solid.

EXAMPLE 4 1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-5-pentylmethacrylate (6)

To a 3-necked, 2-L round-bottomed flask equipped with an overheadstirrer, digital thermometer and a 1-L constant-pressure addition funnelwith a nitrogen inlet was added 590 mL (0.944 mol) of n-butyllithium(1.6 M in hexane). The addition funnel was charged with a solution of107 g (0.47 mol) of 1,1,1-trifluoro-2-trifluoromethyl-2,5-pentanediol(4) in 300 mL of anhydrous THF. The flask was cooled and the diol wasadded dropwise with stirring while maintaining a temperature below 15°C. The resulting yellow-orange solution was stirred for an additional 2hours at which time a solution of 54.5 g (0.52 mol) of methacryloylchloride in 200 mL of anhydrous THF was added dropwise over 1 h at 10°C. The reaction mixture was allowed to reach room temperature overnightafter which it was diluted with 500 mL of diethyl ether and washed with2×500 mL of saturated ammonium chloride and brine, dried over MgSO₄,evaporated and distilled at 74° C. at 1.0 mm Hg (0.5 g of phenothiazinewas added to the pot prior to distillation) to yield 109 g (79%) of thetitle compound. The identity of the product was confirmed using ¹H NMRspectroscopy and HRMS.

EXAMPLE 5 1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-pentylmethacrylate (7)

1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl methacrylate wassynthesized according to the method of Example 4, substituting 142 g(0.63 mol) of 1,1,1-trifluoro-2-trifluoromethyl-2,4-pentanediol (5) for1,1,1-trifluoro-2-trifluoromethyl-2,5-pentanediol (4), and using 793 mL(1.27 mol) of n-butyllithium (1.6M in hexane) and 73 g (0.69 mol) ofmethacryloyl chloride to yield, after distillation at 67° C.@ 1.0 mm Hg,142 g (76%) of the 2° methacrylate as a clear, colorless oil.

EXAMPLE 6 1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-methyl-5-pentylmethacrylate (8)

The title compound was prepared by method of Example 4, substituting 43g (0.181 mol) of1,1,1-trifluoro-2-trifluoromethyl-4-methyl-2,5-pentanediol (2) for1,1,1-trifluoro-2-trifluoromethyl-2,5-pentanediol (4) and 226 mL (0.362mol) of methyllithium (1.6M in ether) in lieu of the n-butyllithium, andusing 20.7 g (0.199 mol) of methacryloyl chloride, to yield 35 g (76%)of the title compound as a clear colorless oil.

EXAMPLE 7 1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-methyl-5-pentylacrylate (9)

1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-methyl-5-pentyl acrylatewas synthesized according to the method of Example 4 but substituting(a) 60 g (0.25 mol) of1,1,1-trifluoro-2-trifluoromethyl-4-methyl-2,5-pentanediol (2) for diol(4), (b) 311 mL (0.497 mol) of methyllithium (1.6M in ether) for then-butyllithium, and (c) 22.3 g (0.248 mol) of acryloyl chloride for themethacryloyl chloride, to yield 58 g (86%) of the title compound as aclear colorless oil.

EXAMPLE 8 1,1,1-Trifluoro-2-hydroxy-2-trifluoromethyl-4-pentylnorbornene-5-carboxylate (11)

(a) Preparation of norbornene-5-carbonylchloride (10): A 1-L, three-neckround-bottom flask equipped with a magnetic stirrer, digitalthermometer, glass stopper, an addition funnel with a nitrogen gaspurge, and a dry-ice cooling bath was charged with freshly distilledcyclopentadiene (248 g, 3.75 mol), which was cooled to 0° C. Theaddition funnel was charged with of freshly distilled acryloyl chloride(317 g, 3.5 mol), which was added dropwise to the reaction over aboutthree hours while maintaining the reaction temperature between 0° C. and10° C. After the acryloyl chloride addition was complete, the coolingbath was removed and the reaction allowed to warm to room temperatureovernight. The reaction mixture was distilled under vacuum, collecting533 g of norbornene-5-carbonylchloride (10), distilling at 54-56° C. ata pressure of 300 milliTorr.

(b) 1,1,1-Trifluoro-2-hydroxy-2-trifluoromethyl-4-pentylnorbornene-5-carboxylate (11): N-butyllithium (1600 ml) (2.56 mol, 1.6Msolution in hexanes) was added to a 3-L, three-necked round bottomedflask equipped with an overhead stirrer, a digital thermometer, a 500-mLcapacity constant-pressure dropping funnel and a nitrogen inlet. Thedropping funnel was charged with a solution of1,1,1-trifluoro-2-trifluoromethyl-2,4-pentanediol (5) (289 g, 1.28 mol)in anhydrous THF (250 ml). The flask was cooled in ice and the THFsolution was slowly added over about 2 hours, while maintaining atemperature below 10° C. Once the addition was complete, the droppingfunnel was recharged with a solution of norbornene-5-carbonylchloride(201 g, 1.28 mol) in anhydrous THF (250 ml), which was then slowly addedover about 1.5 hours, while maintaining a temperature below 10° C. Thesolution was allowed to reach room temperature with stirring overnight.The resulting suspension was transferred to a 4-L separatory funnel andwashed once with water (1 L). The organic layer was separated and theaqueous wash was adjusted to pH 6 (litmus) with concentrated HCl andextracted twice with ether (1 L). The combined organic solutions werewashed once with water and once with brine and dried over anhydrousmagnesium sulfate. The suspension was filtered, the solvent removed on arotary evaporator and the resulting oil distilled twice at 120° C. and0.5 mm Hg to yield 387 g of the title compound as an oil.

EXAMPLE 92-(Cyclopenten-1′-yl)-1,1,1-trifluoro-2-trifluoromethyl-2-propanol (13)

Hexafluoroacetone (105 g, 0.63 mol) was added to a 250 mL bomb cooled to−50° C. containing exo-methylenecyclopentane (50 g, 0.61 mol). The bombwas sealed and warmed by placing in ice water then allowed to come toroom temperature. Negligible pressure increase occurred. Reaction heatedto 50° C. for 1 hour, then cooled in ice bath and opened. Volatilesremoved under light vacuum to give a colorless oil, 27.3 g (90.4%yield).

EXAMPLE 102-(6′,6′-Dimethylbicyclo[3.1]hepten-2′-yl)-1,1,1-trifluoro-2-trifluoromethyl-2-propanol(14)

Beta-pinene (50.9 g, 0.373 mol) was dissolved in chloroform (100 mL) ina 250 mL RB flask under a nitrogen blanket with a dry ice condenser. Tothis was added hexafluoroacetone gas (62 g, 0.37 mol), maintaining thetemperature below 40° C. with a water bath. Reaction was monitored byGC, and additional hexafluoroacetone was added until complete conversionwas obtained. The chloroform was removed under vacuum.

EXAMPLE 111,1,1,7,7,7-Hexafluoro-2,6-bis(trifluoromethyl)-4-methyl-2,6-hept-3-ene-2,6-diol(15)

Hexafluoroacetone (22.6 g) and isobutene (3.4 g) were condensed into a75 mL bomb at −50° C. The bomb was sealed and allowed to rise to roomtemperature, then heated to 50° C. overnight. The next day the materialwas dissolved into diethyl ether to remove from the bomb, and theproduct recovered on a rotary evaporator as a white solid (22.4 g).H-NMR, C-NMR, F-NMR, and GC/MS were used to confirm structure. The H-NMRdata support an internal double bond.

EXAMPLE 123-(Bicyclo[2.2.1]hept-2-ene-2-yl)-1,1,1-trifluoro-2-trifluoromethyl-2-propanol

Hexafluoroacetone (21.0 g) and 2-exo-methylenenorbornane were added to abomb at −50° C., sealed, then brought to room temperature in a waterbath to control the moderate exotherm. The next day the bomb was heatedto 50° C. for 3 hours, then cooled. A colorless liquid (33.5 g) wasrecovered.

1. A fluorinated polyol selected from the group consisting of:


2. The fluorinated polyol of claim 1, wherein the fluorinated polyol hasthe structure


3. The fluorinated polyol of claim 1, wherein the fluorinated polyol hasthe structure


4. The fluorinated polyol of claim 1, wherein the fluorinated polyol hasthe structure


5. The fluorinated polyol of claim 1, wherein the fluorinated polyol hasthe structure


6. The fluorinated polyol of claim 1, wherein the fluorinated polyol hasthe structure